EP1115817B1 - Travail mecanique d'un metal contenant du cuivre ou de l'aluminium - Google Patents

Travail mecanique d'un metal contenant du cuivre ou de l'aluminium Download PDF

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Publication number
EP1115817B1
EP1115817B1 EP99968677A EP99968677A EP1115817B1 EP 1115817 B1 EP1115817 B1 EP 1115817B1 EP 99968677 A EP99968677 A EP 99968677A EP 99968677 A EP99968677 A EP 99968677A EP 1115817 B1 EP1115817 B1 EP 1115817B1
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weight
group
formula
iii
carbon atoms
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EP99968677A
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German (de)
English (en)
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EP1115817A1 (fr
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Rolf Sköld
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Chem Dimension AB
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Chem Dimension AB
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/041—Triaryl phosphates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/042—Metal salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2225/02—Macromolecular compounds from phosphorus-containg monomers, obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles

Definitions

  • the present invention relates to a method for mechanical working of a metal containing copper, aluminum or an alloy thereof.
  • the method is carried out in the presence of an aqueous cooling lubricant containing an alkanol amine.
  • an alkanol amine is used in combination with a phosphate ester or a carboxylic acid.
  • the lubricant is capable of reducing or preventing the corrosion of both metals as well as iron. In addition it also contributes in an essential way to the lubrication.
  • Aluminum and copper and alloys of these metals are among the most common construction metals.
  • the mechanical working is usually performed in the presence of an aqueous cooling lubricant.
  • a disadvantage of many aqueous cooling lubricants is that they frequently contain an iron corrosion inhibitor, such as monoethanolamine, diethanolamine or triethanolamine, which has a detrimental effect on copper, aluminum or alloys thereof and causes discoloration and dissolution. Beside the corrosion, any dissolved metal also constitutes an environmental hazard and is difficult to remove from water in the process of disposal of the cooling lubricant.
  • anionic surface active components with long aliphatic groups such as groups with 14-44 carbon atoms have been used.
  • Exemplary components are phosphate esters and fatty acids and dimer acids.
  • Their protective action depends on the formation of insoluble, organic layers on the metal surfaces. If, however, dissolved di- or trivalent metals exist in the cooling lubricant, the anionic components will form insoluble salts with these metals ions. This may sometimes further increase the corrosion inhibiting effect, but it will also lead to the formation of an undesirable sticky precipitation, which e.g. tend to interfere with the cleaning of the cooling lubricant.
  • Another drawback is the difficulty to remove the hydrophobic layers formed on the metal surfaces. If they are not removed, they will cause problems in the subsequent surface treatment, for example pickling, phosphatizing, galvanizing or other metal depositing processes. The presence of the long chain anionic components may also cause undesirable foaming and scum.
  • US patent 4 315 889 discloses a method of reducing the release of cobalt by performing the metal working in the presence of a cooling lubricant containing, as an active component, a specific triazole or thiadiazole compound.
  • a cooling lubricant containing, as an active component, a specific triazole or thiadiazole compound.
  • active compounds are consumed in the presence of ethanolamines, the aqueous cooling lubricant has to be regularly upgraded.
  • EP-A-0180561 describes the use of a tertiary alkanol amine compound for reducing the release of cobalt.
  • the tertiary alkanol amine compound can advantageously be combined with carboxylic acids for further protection against the release of cobalt and the corrosion of iron.
  • the present invention relates to a process for the mechanical working of metals containing copper, aluminum or alloys thereof, which process is performed in the presence of an aqueous cooling lubricant having a pH of 6-10 and containing an alkanol amine of the formula N(R 3 )(R 4 )(R 5 ) (I), where R 3 , R 4 and R 5 independently of each other designate a group (AO) n H, where AO is an ethyleneoxy group or a propyleneoxy group and n is a number from 2-6, and the number of ethyleneoxy groups in relation to the number of propyleneoxy groups is between 2:1 and 1:3.
  • aqueous cooling lubricants in which the alkanol amine I are supplemented by a short chain anionic compound selected from the group consisting of a phosphate ester of the formula R 1 (oxyalkylene) n OP(O)(X)(OH) (II) or (HO) 2 (O)P-(oxyalkylene) m -OP(O)(OH) 2 (III), where R 1 is an alkyl group with 1-12 carbon atoms, X is hydroxyl or the group R 1 O, where R 1 has the above mention meaning, oxyalkylene is a group containing 2-4 carbon atoms, n is a number from 1-15 and m is a number from 4- 20, or a salt thereof, or a carboxylic acid of the formula R 2 (COOH) p (IV), where R 2 is an alkyl group with 4-10 carbon atoms and p is 1 or 2,
  • the total amount of the anionic compounds II, III and IV is normally 10-1000%, preferably 15-300% by weight of the alkanol amine I.
  • the alkanol amine I preferably in combination with at least one of the anionic compounds II, III and IV, results in an essential reduction in the amount of dissolved copper and discolored copper and aluminum in comparison with a corrosion inhibitor consisting of a carboxylic acid and an alkanol amine, such as triethanolamine.
  • the compounds I, II, III and IV also contribute to the lubrication.
  • the cooling lubricant suitably contains at least one of the phosphate esters of formula II or III and a carboxylic acid of formula IV.
  • the alkanol amine I contains always at least 2 propyleneoxy groups.
  • the alkanol amines are produced by ethoxylation of ammonia with 2-4 moles ethylene oxide followed by propoxylation with 4-7 moles per mole ammonia.
  • the hydroxyl groups of these alkanol amines will consist of only secondary hydroxyl groups.
  • the ratio of ethyleneoxy groups to propyleneoxy groups is preferably between 1:1 and 1:3.
  • the carboxylic acid of formula IV contains an aliphatic group which can be saturated or unsaturated, straight or branched.
  • the aliphatic group of monocarboxylic acids contains 5-9 carbon atoms, while the dicarboxylic acids preferably have an aliphatic group with 6-10 carbon atoms.
  • Suitable examples of carboxylic acids are azelaic acid, pelargonic acid, sebacic acid, isononanoic acid, neodecanoic acid, n-octanoic acid, n-decanoic acid and dodecandioic acid.
  • the carboxylic acids having a branched aliphatic group of the preferred size are often utilized, since they are low foaming.
  • the (oxyalkylene) n group and (oxyalkylene) m group respectively are suitable selected in such a way that the esters will be water-soluble or easily dispersible in water.
  • the aliphatic group R 1 can be saturated or unsaturated, straight or branched and contains preferably 2-8 carbon atoms.
  • the phosphate ester with formula II consists of at least 50% by weight of monoesters.
  • the polyoxyalkylene chain preferably consists, at least partially, of oxyalkylene groups with 3-4 carbons atoms and m preferably is at least 6, since these diphosphate esters beside the corrosion inhibiting effect give a considerable contribution to the lubrication.
  • the content of the alkanol amine I and the anionic compounds II, III and IV may vary within wide limits, but is normally between 0.1 and 10% by weight, preferably between 1 and 7% by weight of the cooling lubricant ready for use.
  • the cooling lubricant can also contain a number of other additives, such as additional corrosion-inhibiting additives and lubricants, pH-regulating or controlling additives, bactericidal agents, viscosity-increasing additives, solubilizers, perfumes, colourants etc.
  • additional corrosion inhibitors examples include amines compounds, such as triazole and thiadiazole compounds, and inorganic compounds, such as alkali metal hydroxides and boric acid, and reaction products between boric acid and/or carboxylic acids with organic compounds, such as alkanol amines.
  • the content of these additional corrosion inhibitors may be up to 3% by weight of the cooling lubricant.
  • cooling lubricant containing the alkanolamine I and the anionic surfactants II, III and IV has an adequate lubrication ability for most applications it may be occasions where improved lubrication is desired.
  • suitable lubricants to be incorporated into a cooling lubricant according to the invention are those selected from the group consisting of esters or amides of mono- or dicarboxylic acids having at least 12 carbon atoms in the acyl groups, aliphatic phosphate esters containing one or two aliphatic groups with 6-18 carbon atoms, nonionic alkylene oxide adducts with a molecular weight above 400, such as polypropylene glycols, glycols of randomly distributed propyleneoxy and ethyleneoxy groups and block polymers of propylene oxide and ethylene oxide, and mixtures thereof.
  • the content of these additional lubricants may be up to 3% by weight of the cooling lubricant ready for use.
  • the solubilizers are usually low molecular compounds containing at least one hydroxyl.
  • the molecular weight is normally below 400.
  • suitable solubilizers are propypeneglycol, ethylene diethyleneglycol, butyl diethyleneglycol and butyl triethyleneglycol.
  • a typical concentrate according to the invention has the following composition: alkanol amine I 20-95, preferably 50-90% by weight anionic compounds II, III and IV 0-60, preferably 10-50% by weight additional corrosion inhibitors 0-30, preferably 0-15% by weight additional lubricants 0-30, preferably 0-15% by weight water 5-80, preferably 10-50% by weight other ingredients 0-30, preferably 0-15% by weight
  • the total amount of the additional corrosions inhibitors and lubricants and other ingredients is often 5-40% by weight of the concentrate. Before the concentrate is used, it is diluted with water so that the cooling lubricant ready for use will have a total content of 0.5-20% by weight, preferably 2-10% by weight.
  • the present invention is further illustrated by the following Examples.
  • Cooling lubricants ready for use were prepared from the aqueous concentrates in the Table 1 below.
  • the content of water was 30% by weight.
  • the pH of the concentrates was adjusted to 9 by adding KOH before they were diluted with water to an active content of 4% by weight.
  • the corrosion inhibiting effects on copper and iron of these fluids were determined at an ambient temperature of 22°C by the following test methods.
  • Cu-corrosion tests were performed by assessing the amount of leached copper obtained, when a 20 ml glass vial containing 5 glass beads, 5 mg of fine powder of copper and 10 ml of one of the fluids was shaken for 7 days. The amount of copper dissolved was measured by use of an atomic absorption spectrophotometer (AAS). Initial screening of the fluids was done by using analytical sticks from Merck and only samples, which were found to contain less than 30 ppm of copper, were subjected to AAS analysis.
  • AAS atomic absorption spectrophotometer
  • the metal working fluids formulated according to the invention namely compositions 2-4, 6-8, 10-12, 14-16, 18-20, 22-24, 26-28 and 30-32 have excellent corrosion inhibiting properties as regards copper and are superior to the comparison fluids 1, 5, 9, 13, 17, 21, 25 and 29.
  • the iron corrosion inhibiting properties of the formulations according to the invention are acceptable and in all tests zero iron corrosion were obtained, when the concentration of the active components was raised to 5,5% by weight.
  • compositions with their numbers corresponds to the compositions in Example 1.
  • Table 3 Composition no Brass 1 4 5 8 9 12 - corrosion degree 5 0 5 0 5 1 - solution blue - blue - blue - Aluminum 5 0 5 0 5 0

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)

Claims (9)

  1. Procédé pour usiner mécaniquement un métal contenant du cuivre, de l'aluminium ou un alliage de ceux-ci, comprenant l'utilisation d'un lubrifiant refroidissant aqueux ayant un pH entre 6 et 10 et contenant une alcanolamine de formule

            N(R3)(R4)(R5)     (I),

    où R3, R4 et R5, indépendamment les uns des autres, désignent un groupe (AO)nH, où AO est un groupe éthylèneoxy ou un groupe propylèneoxy et n est un nombre de 2 à 6, le nombre de groupes éthylèneoxy par rapport au nombre de groupes propylèneoxy étant entre 2:1 et 1:3.
  2. Procédé selon la revendication 1, dans lequel l'alcanolamine I a trois groupes hydroxyles secondaires.
  3. Procédé selon la revendication 2, dans lequel l'alcanolamine est obtenue en éthoxylant 1 mole d'ammoniac avec 2 à 4 moles d'oxyde d'éthylène puis en propoxylant avec 4 à 7 moles d'oxyde de propylène.
  4. Procédé selon la revendication 1, 2 ou 3, dans lequel le lubrifiant contient aussi un composé anionique choisi dans le groupe constitué par un ester phosphate de formule

            R1(oxyalkylène)nOP(O)(X)(OH)     (II),

    ou

            (HO)2(O)P-(oxyalkylène)m-OP(O)(OH)2     (III),

       où R1 est un groupe alkyle ayant 1 à 12 atomes de carbone, X est un groupe hydroxyle ou le groupe R1O, où R1 a la signification susmentionnée, oxyalkylène est un groupe contenant 2 à 4 atomes de carbone, n est un nombre de 1 à 15 et m est un nombre de 4 à 20, ou un sel de celui-ci, ou un acide carboxylique de formule

            R2(COOH)p     (IV),

       où R2 est un groupe alkyle ayant 6 à 12 atomes de carbone et p vaut 1 ou 2, ou un sel de celui-ci, ou un mélange de ceux-ci.
  5. Procédé selon la revendication 4, dans lequel l'ester phosphate III contient une chaîne polyoxyalkylène, qui consiste au moins partiellement en groupes oxyalkylènes ayant 3 à 4 atomes de carbone, et l'ester phosphate II consiste en au moins 50 % en poids de monoesters.
  6. Procédé selon la revendication 3, dans lequel l'acide carboxylique de formule IV est un acide monocarboxylique, où R2 est un groupe aliphatique ramifié ayant 5 à 9 atomes de carbone ou un acide dicarboxylique, où R2 est un groupe aliphatique ramifié ayant 6 à 10 atomes de carbone.
  7. Procédé selon l'une quelconque des revendications 3 à 6, dans lequel le lubrifiant refroidissant contient au moins un ester phosphate de formule II ou III et un ester carboxylique de formule IV.
  8. Concentré selon la revendication 7, caractérisé en ce qu'il a la composition suivante : alcanolamine I 50-90 % en poids composés anioniques II, III et IV 10-50 % en poids inhibiteurs de corrosion supplémentaires 0-15 % en poids lubrifiants supplémentaires 0-15 % en poids autres ingrédients 0-15 % en poids eau 10-50 % en poids,
    où l'alcanolamine I et les composés anioniques II, III et IV ont la même signification que celle définie dans les revendications 1 à 6, les composés anioniques comprennent au moins un ester phosphate de formule II ou III et un acide carboxylique de formule IV.
  9. Concentré selon les revendications 7 ou 8, caractérisé en ce que la quantité totale d'inhibiteurs de corrosion supplémentaires et de lubrifiants et autres ingrédients est de 5 à 40 % en poids.
EP99968677A 1998-09-07 1999-09-03 Travail mecanique d'un metal contenant du cuivre ou de l'aluminium Expired - Lifetime EP1115817B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
SE9803005A SE514315C2 (sv) 1998-09-07 1998-09-07 Ett förfarande för mekanisk bearbetning av en metall, som innehåller koppar eller aluminium
SE9803005 1998-09-07
PCT/SE1999/001521 WO2000014191A1 (fr) 1998-09-07 1999-09-03 Travail mecanique d'un metal contenant du cuivre ou de l'aluminium

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EP1115817A1 EP1115817A1 (fr) 2001-07-18
EP1115817B1 true EP1115817B1 (fr) 2004-12-29

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Country Status (6)

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US (1) US6602833B1 (fr)
EP (1) EP1115817B1 (fr)
AT (1) ATE286114T1 (fr)
DE (1) DE69922975T2 (fr)
SE (1) SE514315C2 (fr)
WO (1) WO2000014191A1 (fr)

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Publication number Priority date Publication date Assignee Title
SE516115C2 (sv) * 1999-01-18 2001-11-19 Rolf Skoeld Förfarande och ett koncentrat för mekanisk bearbetning av metaller eller legeringar
FR2832160B1 (fr) * 2001-11-15 2005-01-14 Atofina PROCEDE DE TRAVAIL OU MISE EN FORME DES METAUX EN PRESENCE DE LUBRIFIANTS AQUEUX A BASE D'ACIDE METHANESULFONIQUE (AMS) ou D'UN SEL HYDROSOLUBLE D'AMS
WO2006023880A2 (fr) * 2004-08-23 2006-03-02 Isis Pharmaceuticals, Inc. Composes et procedes permettant de caracteriser les oligonucleotides
US20060160707A1 (en) * 2005-01-19 2006-07-20 Steven E. Rayfield. Aluminum metal machining fluid lubricating concentrate
US20090206526A1 (en) * 2008-02-18 2009-08-20 Huntsman Petrochemical Corporation Sintering aids
JP5693463B2 (ja) * 2008-12-04 2015-04-01 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 片面または両面に亜鉛メッキされた鋼板から成形品を製造する方法

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US4313836A (en) 1980-12-01 1982-02-02 Basf Wyandotte Corporation Water-based hydraulic fluid and metalworking lubricant
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SE445357B (sv) * 1984-10-30 1986-06-16 Berol Kemi Ab Forfarande vid mekanisk bearbetning av kobolthaltig metall samt koncentrat avsett att efter spedning med vatten anvendas vid forfarandet
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BR9306999A (pt) * 1992-09-04 1999-01-12 Henkel Corp Aditivo de lubrificante adequado para combinação com uma mistura de revestimento de papel ou papelão composição de revestimento de papel ou paprelão e processo para aplicar uma composição de revestimento a base de água a uma tela de papel ou papelão
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Also Published As

Publication number Publication date
DE69922975T2 (de) 2005-12-08
ATE286114T1 (de) 2005-01-15
WO2000014191A1 (fr) 2000-03-16
DE69922975D1 (de) 2005-02-03
US6602833B1 (en) 2003-08-05
SE514315C2 (sv) 2001-02-12
EP1115817A1 (fr) 2001-07-18
SE9803005D0 (sv) 1998-09-07
SE9803005L (sv) 2000-03-08

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